N-substituted tetrahydropyridines and their use as pesticides

ABSTRACT

A description is given of compounds of the formula  
                 
 
     in which  
     R 1  and R 2  independently of one another are halogen, C 1 -C 6 alkyl, halo-C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halo-C 1 -C 6 alkoxy, or SF 5 ,  
     R 3  is hydrogen, OH, halogen, C 1 -C 6 alkoxy or —O—C(═O)—C 1 -C 6 alkyl,  
     R 4  is for example hydrogen, halogen, C 1 -C 6 alkyl, halo-C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halo-C 1 -C 6 alkoxy or SCN;  
     R 5  and R 6  independently of one another are for example hydrogen, C 1 -C 12 alkyl, halo-C 1 -C 12 alkyl, C 2 -C 12 alkenyl, halo-C 2 -C 12 alkenyl or C 2 -C 12 alkynyl; and  
     q is  0  or  1;    
     and, where appropriate, E/Z isomers, E/Z isomer mixtures and/or tautomers, each in free form or in salt form;  
     a process for the preparation of these compounds and their use, pesticide compositions whose active ingredient is selected from these compounds, or an agrochemically useable salt thereof, a process for preparing these compositions, and their use, plant propagation material treated with these compositions, and a method of combating pests.

[0001] The present invention provides

[0002] (1) a compound of the formula

[0003] in which

[0004] R₁ and R₂ independently of one another are halogen, C₁-C₆alkyl,halo-C₁-C₆alkyl, C₁-C₆alkoxy, halo-C₁-C₆alkoxy, —S(═O)_(p)-R₉ or SF₅,

[0005] R₃ is hydrogen, OH, halogen, C₁-C₆alkoxy or —O—C(═O)—C₁-C₆alkyl,

[0006] R₄ is hydrogen, halogen, C₁-C₆alkyl, halo-C₁-C₆alkyl,C₁-C₆alkoxy, halo-C₁-C₆alkoxy, —S(═O)_(p)-R₉ or SCN;

[0007] R₅ and R₆ independently of one another are hydrogen, C₁-C₁₂alkyl,halo-C₁-C₁₂alkyl, C₂-C₁₂alkenyl, halo-C₂-C₁₂alkenyl, C₂-C₁₂alkynyl,halo-C₂-C₁₂alkynyl, C₃-C₈cycloalkyl, —C(═O)—O—R₇, —C(═S)—O—R₈,—C(═Y)—Z—R₈, —S(═O)_(p)-R₉, aryl, aryl-C₁-C₆alkyl, heterocyclyl orheterocyclyl-C₁-C₆alkyl; or, depending on substitution possibilities onthe ring are C₃-C₈cycloalkyl, aryl, aryl-C₁-C₆alkyl, heterocyclyl orheterocyclyl-C₁-C₆alkyl, substituted from one to five timesindependently of one another by halogen, hydroxyl, cyano, nitro,C₁-C₆alkyl, halo-C₁-C₆alkyl, C₁-C₆alkoxy or halo-C₁-C₆alkoxy; or

[0008] in common, together with the nitrogen atom to which they areattached, form a heterocyclic ring which is unsubstituted orsubstituted;

[0009] Y is oxygen or sulfur;

[0010] Z is a bond, —NR₁₀— or sulfur;

[0011] R₇ is C₁-C₆alkoxy-C₁-C₆alkyl, C₁-C₆alkylthio-C₁-C₆alkyl,C₁-C₆alkylamino-C₁-C₆alkyl, C₃-C₆alkynyl,C₁-C₆alkyl-S(═O)_(p)—C₁-C₆alkyl, C₃-C₈cycloalkyl, aryl, aryl-C₁-C₆alkyl,heterocyclyl or heterocyclyl-C₁-C₆alkyl; or, depending on substitutionpossibilities on the ring is C₃-C₈cycloalkyl, aryl, aryl-C₁-C₆alkyl,heterocyclyl or heterocyclyl-C₁-C₆alkyl, substituted from one to fivetimes independently of one another by halogen, cyano, nitro, C₁-C₆alkyl,halo-C₁-C₆alkyl, C₁-C₆alkoxy or halo-C₁-C₆alkoxy;

[0012] R₈ is C₁-C₆alkyl, halo-C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkyl,C₁-C₆alkylthio-C₁-C₆alkyl, C₂-C₆alkenyl, C₃-C₆alkynyl,C₁-C₆alkyl-S(═O)_(p)—C₁-C₆alkyl, C₃-C₈cycloalkyl, aryl, aryl-C₁-C₆alkyl,heterocyclyl or heterocyclyl-C₁-C₆alkyl; or, depending on substitutionpossibilities on the ring, is C₃-C₈cycloalkyl, aryl, aryl-C₁-C₆alkyl,heterocyclyl or heterocyclyl-C₁-C₆alkyl substituted from one to fivetimes independently of one another by halogen, cyano, nitro, C₁-C₆alkyl,halo-C₁-C₆alkyl, C₁-C₆alkoxy or halo-C₁-C₆alkoxy;

[0013] R₉ is C₁-C₆alkyl, C₃-C₈cycloalkyl, halo-C₁-C₆alkyl or benzyl;

[0014] R₁₀ is hydrogen, C₁-C₆alkyl, C₃-C₈cycloalkyl, halo-C₁-C₆alkyl orbenzyl;

[0015] p is 0, 1 or 2; and

[0016] q is 0 or 1;

[0017] and, where appropriate, E/Z isomers, E/Z isomer mixtures and/ortautomers, each in free form or in salt form;

[0018] a process for the preparation of these compounds and their use,pesticide compositions whose active ingredient is selected from thesecompounds, or an agrochemically useable salt thereof, a process andintermediates for preparing these compositions, and their use, plantpropagation material treated with these compositions, and a method ofcombating pests.

[0019] The literature proposes certain piperidine derivatives as activeingredients in pesticide compositions. The biological properties ofthese known compounds are, however, unable to provide full satisfactionin the field of pest control, and so there is a need to provide furthercompounds having pesticidal properties, particularly for the control ofinsects and representatives of the order Acarina, this object beingachieved in accordance with the invention through the provision of thepresent compounds of the formula (I).

[0020] The compounds of the formula (I) and, where appropriate, theirtautomers may form salts, e.g. acid addition salts. These salts areformed, for example, with strong inorganic acids, such as mineral acids,e.g. sulfuric acid, a phosphoric acid or a hydrohalic acid, with strongorganic carboxylic acids, such as C₁-C₄alkanecarboxylic acids,unsubstituted or substituted, for example by halogen, e.g. acetic acid,such as saturated or unsaturated dicarboxylic acids. e.g. oxalic,malonic, maleic, fumaric or phthalic acid, such as hydroxycarboxylicacids, e.g. ascorbic, lactic, malic, tartaric or citric acid, or such asbenzoic acid, or with organic sulfonic acids, such asC₁-C₄alkanesulfonic or arylsulfonic acids, unsubstituted or substituted,for example by halogen, e.g. methanesulfonic or p-toluenesulfonic acid.Furthermore, compounds of the formula (I) containing at least on acidicgroup may form salts with bases. Suitable salts with bases are, forexample, metal salts, such as alkali metal or alkaline earth metalsalts, e.g. sodium, potassium or magnesium salts, or salts with ammoniaor with an organic amine, such as morpholine, piperidine, pyrrolidine, amono-, di- or tri-lower alkylamine, e.g. ethyl-, diethyl-, triethyl- ordimethylpropylamine, or a mono-, di- or trihydroxy-lower alkylamine,e.g. mono-, di- or triethanolamine. Furthermore, corresponding innersalts may be formed where appropriate. Preference is given on the onehand to the free form. Among the salts of compounds of the formula (I),the agrochemically advantageous salts are preferred. Above and below,references to the free compounds of the formula (I) and/or their saltsshould also be understood where appropriate as referring to thecorresponding salts, and, conversely, references to the salts should beunderstood to include the free compounds of the formula (I). Similarcomments apply to tautomers of compounds of the formula (I) and theirsalts.

[0021] The general terms used above and below, unless differentlydefined, have the meanings set out below.

[0022] Halogen (halo), as a group per se and also as a structuralelement of other groups and compounds, such as of haloalkyl,halocycloalkyl, haloalkenyl, haloalkynyl and haloalkoxy, is fluorine,chlorine, bromine or iodine, especially fluorine, chlorine or bromine,but particularly fluorine or chlorine, especially chlorine.

[0023] Carbon-containing groups and compounds contain, unlessdifferently defined, in each case from 1 up to and including 20,preferably from 1 up to and including 18, in particular from 1 up to andincluding 10, especially from 1 up to and including 6, in particularfrom 1 up to and including 4, especially from 1 up to and including 3,in particular 1 or 2, carbon atoms; methyl is very particularlypreferred.

[0024] Alkyl, as a group per se and also as a structural element ofother groups and compounds, such as, for example, of haloalkyl, alkoxy,alkoxyalkyl, haloalkoxy, alkoxycarbonyl, alkylthio, haloalkylthio,alkylsulfonyl and alkylsulfonyloxy, in each case with appropriateaccount being taken of the particular number of carbon atoms present inthe corresponding group or compound, is either straight-chain, e.g.methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl,n-hexadecyl or n-octadecyl, or branched, e.g. isopropyl, isobutyl,sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl.

[0025] Alkenyl and alkynyl, as groups per se and also as structuralelements of other groups and compounds, such as of haloalkenyl,haloalkynyl, alkenyloxy, haloalkenyloxy, alkynyloxy or haloalkynyloxy,are straight-chain or branched and contain in each case two orpreferably one unsaturated carbon-carbon bond(s). By way of example,mention may be made of vinyl, prop-2-en-1-yl, 2-methylprop-2-en-1-yl,but-2-en-1-yl, but-3-en-1-yl, prop-2-yn-1-yl, but-2-yn1-yl andbut-3-yn-1-yl.

[0026] Cycloalkyl, as a group per se and also as a structural element ofother groups and compounds, such as, for example, of alkyl, iscyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl andcyclooctyl. Preference is given to cyclopentyl and cyclohexyl,especially cyclopropyl.

[0027] Halogen-substituted carbon-containing groups and compounds, suchas haloalkyl and haloalkoxy, may be partly halogenated orperhalogenated, the halogen substituents in the case of multiplehalogenation being identical or different. Examples of haloalkyl, as agroup per se and also as a structural element of other groups andcompounds, such as of haloalkoxy, are methyl substituted from one tothree times by fluorine, chlorine and/or bromine, such as CHF₂, CF₃ orCH₂Cl; ethyl substituted from one to five times by fluorine, chlorineand/or bromine, such as CH₂CF₃, CF₂CF₃, CF₂CCl₃, CF₂CHCl₂, CF₂CHF₂,CF₂CFCl₂, CH₂CH₂Cl, CF₂CHBr₂, CF₂CHClF, CF₂CHBrF or CClFCHClF; propyl orisopropyl substituted from one to seven times by fluorine, chlorineand/or bromine, such as CH₂CHBrCH₂Br, CF₂CHFCF₃, CH₂CF₂CF₃, CF₂CF₂CF₃,CH(CF₃)₂ or CH₂CH₂CH₂Cl; and butyl or one of its isomers substitutedfrom one to nine times by fluorine, chlorine and/or bromine, such asCF(CF₃)CHFCF₃, CF₂(CF₂)₂CF₃ or CH₂(CF₂)₂CF₃.

[0028] Aryl is particularly phenyl or naphthyl; phenyl is preferred.

[0029] Heterocyclyl is a 5- to 7-membered saturated or unsaturated,preferably aromatic, ring having from one to four heteroatoms selectedfrom the group consisting of N, O and S. Preference is given to aromatic5- and 6-membered rings containing a nitrogen heteroatom and, ifdesired, a further heteroatom, preferably nitrogen, oxygen or sulfur,especially nitrogen and oxygen. Preferred heterocyclyl radicals are, forexample, pyrrolyl, pyazolyl [sic], imidazolyl, 1,2,4-triazolyl,tetrazolyl, pyrazinyl, pyridyl, pyrimidinyl, pyridazinyl, oxadiazinanyl,thiazolyl, thiadiazinyl, isothiazolyl, isoxazolyl, indolyl, indazolyl,benzimidazolyl, benzothiazolyl, furanyl, tetrahydrofuranyl and thienyl.

[0030] Preferred embodiments in the context of the invention are

[0031] (2) Compounds as per (1) of the formula (I) in which R₁ and R₂independently of one another are halogen, C₁-C₂alkyl, halo-C₁-C₂alkyl,C₁-C₂alkoxy or halo-C₁-C₂alkoxy;

[0032] in particular, are independently of one another fluorine,chlorine, methyl, trifluoromethyl, methoxy or trifluoromethoxy;

[0033] especially are independently of one another fluorine,trifluoromethyl or trifluoromethoxy;

[0034] with very particular preference, in which R₁ and R₂ aretrifluoromethyl;

[0035] (3) Compounds as per (1) or (2) of the formula (I) in which R₃ ishydrogen, OH, halogen or C₁-C₆alkoxy;

[0036] in particular is hydrogen, OH, fluorine or methoxy;

[0037] especially, is hydrogen or OH; with very particular preference,is OH;

[0038] (4) Compounds as per (1) to (3) of the formula (I) in which R₄ ishydrogen, chlorine, fluorine, methoxy, trifluoromethyl ortrifluoromethoxy; in particular is hydrogen;

[0039] (5) Compounds as per (1) to (4) of the formula (I) in which

[0040] R₅ is C₁-C₆alkyl, C₃-C₁₂alkenyl, C₃-C₁₂alkynyl, C₃-C₈cycloalkyl,—C(═O)—O—R₇, —C(═S)—O—R₈, —C(═Y)—Z—R₈, —S(═O)_(p)-R₉, phenyl-C₁-C₆alkyl,or phenyl-C₁-C₆alkyl substituted from one to three times independentlyof one another by halogen, cyano, nitro, halo-C₁-C₆alkyl orhalo-C₁-C₆alkoxy;

[0041] preferably is —C(═O)—O—R₇, —C(═S)—O—R₈, —C(═Y)—Z—R₈,—S(═O)_(p)-R₉ or phenyl-C₁-C₆alkyl;

[0042] (6) Compounds as per (1) to (4) of the formula (I) in which R₅ isC₃-C₁₂alkynyl, especially C₃alkynyl;

[0043] (7) Compounds as per (1) to (4) of the formula (I) in which R₅ is—C(═O)—O—R₇ and

[0044] R₇ is C₁-C₂alkoxy-C₁-C₂alkyl, C₃-C₆alkynyl,C₁-C₂alkyl-S(═O)_(p)—C₁-C₆alkyl, C₃-C₈cycloalkyl, phenyl, or benzyl,

[0045] in particular is C₃-C₆alkynyl, especially —CH₂—C≡CH;

[0046] (8) Compounds as per (1) to (4) of the formula (I) in which R₅ is—C(═S)—O—R₈ and

[0047] R₈ is C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkyl, C₂-C₆alkenyl,C₃-C₆alkynyl, C₃-C₈cycloalkyl, phenyl or benzyl;

[0048] (9) Compounds as per (1) to (4) of the formula (I) in which R₅ is—C(═O)—Z—R₈,

[0049] Z is sulfur, and

[0050] R₈ is C₁-C₆alkyl, halo-C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkyl,C₁-C₆alkylthio-C₁-C₆alkyl, C₂-C₆alkenyl, C₃-C₆alkynyl, C₃-C₈cycloalkyl,phenyl or benzyl;

[0051] (10) Compounds as per (1) to (4) of the formula (I) in which R₅is —C(═Y)—Z—R₈,

[0052] Z is a bond;

[0053] Y is O or S, preferably O; and

[0054] R₈ is C₁-C₆alkyl, halo-C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkyl,C₁-C₆alkylthio-C₁-C₆alkyl, C₂-C₆alkenyl, C₃-C₆alkynyl, C₃-C₈cycloalkyl,phenyl or benzyl;

[0055] (11) Compounds as per (1) to (4) of the formula (I) in which R₅is —C(═Y)—Z(NR₁₀)-R₈,

[0056] Y is O or S, preferably O;

[0057] R₈ is C₁-C₆alkyl, halo-C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkyl,C₁-C₆alkylthio-C₁-C₆alkyl, C₂-C₆alkenyl, C₃-C₆alkynyl, C₃-C₈cycloalkyl,phenyl or benzyl; and

[0058] R₁₀ is hydrogen or C₁-C₆alkyl, especially hydrogen;

[0059] (12) Compounds as per (1) to (4) of the formula (I) in which R₅is —S(═O)_(p)-R₉;

[0060] R₉ is C₁-C₆alkyl, halo-C₁-C₆alkyl, C₃-C₈cycloalkyl or benzyl;especially C₁-C₂alkyl or halo-C₁-C₂alkyl; and

[0061] p is 2;

[0062] (13) Compounds as per (1) to (4) of the formula (I) in which

[0063] R₅ is phenyl or phenyl which is substituted once or twiceindependently of one another by halogen, trifluoromethyl ortrifluoromethoxy;

[0064] (14) Compounds as per (1) to (13) of the formula (I) in which

[0065] R₆ is hydrogen, C₁-C₆alkyl, C₃-C₈cycloalkyl or benzyl; especiallyC₁-C₆alkyl, or hydrogen; very particularly hydrogen;

[0066] (15) Compounds as per 1) to 14) of the formula (I) in which q is1;

[0067] (16) Compounds as per 1) to 3) of the formula (I) in which

[0068] R₅ and R₆ jointly, together with the nitrogen atom to which theyare attached, form a heterocyclic ring which is unsubstituted orsubstituted.

[0069] Particular preference is given in the context of the invention tothe compounds of the formula (I) that are listed in the Tables.

[0070] The invention further provides a process for preparing thecompounds of the formula (I), or a salt thereof, which comprises

[0071] (a) for preparing a compound of the formula (I) in which q is 0,treating a compound of the formula

[0072] in which R₁, R₂, R₃, R₄, R₅ and R₆ are as defined above forformula (I) and X is a counterion such as halogen, sulfate or phosphatewith a reducing agent such as NaBH₄, for example, in the absence orpresence of a solvent which is inert under the chosen reactionconditions, and, if desired,

[0073] (b) for preparing a compound of the formula (I) in which q is 1,reacting the resultant compound of the formula (I) in which q is 0,where appropriate, with an oxidizing agent, especially H₂O₂.

[0074] The invention additionally provides a process for preparing acompound of the formula (II) or a salt thereof, which comprises

[0075] (c) if R₁ and R₂ are identical, reacting a compound of theformula

[0076] which is known or may be prepared by conventional processes andin which R is C₁-C₁₂alkyl or benzyl with two moles of a compound of theformula

[0077] which is known or may be prepared by conventional processes andin which R₁ is as defined above for formula (I) in the presence ofmagnesium or n-butyllithium; and

[0078] (d) reacting the resultant compound of the formula

[0079] in which R₁ is as defined above for formula (I), and which isknown or may be prepared by conventional processes, with a compound ofthe formula

[0080] in which R₄, R₅ and R₆ are as defined above for formula (I) and Xis a leaving group, preferably chlorine or bromine.

[0081] The invention additionally provides a process for preparingcompounds of the formula (I) as defined above and in which q is 0, or asalt thereof, which comprises

[0082] (e) for preparing a compound of the formula (I) in which R₁ andR₂ are identical or different, R₃ is OH and q is 0, reacting a compoundof the formula (IV) with isonicotinonitrile in the presence of magnesiumor n-butyllithium and reacting the compound obtained following acidichydrolysis, of the formula

[0083] in which R₁ is as defined above for the formula (I), and which isknown per se, with a compound of the formula

[0084] which is known or may be prepared by conventional processes, andin which R₂ is as defined above for formula (I), in the presence ofmagnesium or n-butyllithium; and further reacting the resulting compoundof the formula

[0085] which is known and in which R₁ and R₂ are as defined above forthe formula (I) in analogy to process steps (d), (a) and, whereappropriate, (b) to give a compound of the formula (I); or

[0086] (f) for preparing a compound of the formula (I) in which R₃ ishydrogen, reacting a compound of the formula (IX) with a reducing agentsuch as triethylsilane, for example, in the presence of trifluoroaceticacid or trifluoromethanesulfonic acid to give a compound of the formula

[0087] which is known per se and in which R₁ and R₂ are as defined abovefor the formula (I) and further reacting this compound of the formula(X) in analogy to process steps (d), (a) and, where appropriate, (b);

[0088] (g) for preparing a compound of the formula (I) in which R₃ isalkoxy, further reacting a compound of the formula (IX) with an alkylhalide in the presence of a strong base, such as sodium hydride, forinstance, to give a compound of the formula

[0089] which is known per se and in which R₁ and R₂ are as defined abovefor the formula (I), and further reacting this compound of the formula(XI) in analogy to process steps (d), (a) and, where appropriate, (b) togive a compound of the formula (I);

[0090] and/or, if desired, converting a compound of the formula (I) infree form or in salt form, obtainable in accordance with the process orotherwise, into another compound of the formula (I), resolving an isomermixture obtainable in accordance with the process and isolating thedesired isomer, and/or converting a free compound of the formula (I)obtainable in accordance with the process or otherwise into a salt orconverting a salt of a compound of the formula (I) obtainable inaccordance with the process or otherwise into the free compound of theformula (I) or into another salt.

[0091] The invention further provides a process for preparing a compoundof the formula (I) as defined above, which comprises

[0092] (h) in analogy to the above-described process steps (c) to (g),preparing a compound of the formula

[0093] in which R₁, R₂, R₃, R₄ and X are defined above for formula (I),and in which instead of a compound of the formula (VI) in process step(d) a compound of the formula

[0094] in which R₄ and X are as defined for formula (VI), and which isknown or may be prepared by conventional processes, is used;

[0095] (i) reducing the resulting compound of the above formula (XII) inanalogy to the above process step (a) to a compound of the formula

[0096] in which R₁, R₂, R₃, and R₄ are as defined above for formula (I);

[0097] (j) reducing the resulting compound of the formula (XIV) withhydrogen in the presence of a hydrogenation catalyst, preferably Raneynickel, to a compound of the formula

[0098] in which R₁, R₂, R₃, and R₄ are as defined above for formula (I);and

[0099] (k) for preparing a compound of the formula (I) in which R₅ isunsubstituted or halogenated C₁-C₁₂alkyl, unsubstituted or halogenatedC₂-C₁₂alkenyl, unsubstituted or halogenated C₂-C₁₂alkynyl,C₃-C₈cycloalkyl, C(═O)—O—R₇, C(═S)—O—R₈, C(═Y)—R₈, S(═O)_(p)-R₉, aryl,aryl-C₁-C₆alkyl, heterocyclyl or heterocyclyl-C₁-C₆alkyl; or isunsubstituted or substituted C₃-C₈cycloalkyl, aryl, aryl-C₁-C₆alkyl,heterocyclyl or heterocyclyl-C₁-C₆alkyl; and

[0100] R₆ is hydrogen, and R₇, R₈, R₉ and p are as defined above;

[0101] reacting the compound of the formula (Ia) with unsubstituted orhalogenated Q-C₁-C₁₂alkyl, unsubstituted or halogenated Q-C₂-C₁₂alkenyl,unsubstituted or halogenated Q-C₂-C₁₂alkynyl, Q-C₃-C₈cycloalkyl,Q-C(═O)—O—R₇, Q-C(═S)—O—R₈, Q-C(═Y)—R₈, Q-S(═O)_(p)-R₉, Q-aryl,aryl-C₁-C₆alkyl [lacuna], Q-heterocyclyl or heterocyclyl-C₁-C₆alkyl-Q;or unsubstituted or substituted Q-C₃-C₈cycloalkyl, Q-aryl,aryl-C₁-C₆alkyl-Q, Q-heterocyclyl or heterocyclyl-C₁-C₆alkyl-Q, in whichQ is a leaving group, and R₇, R₈, R₉ and p are as defined above; or

[0102] (l) for preparing a compound of the formula (I) in which R₅ hasthe definitions indicated under process variant (k) and R₆ isC₁-C₁₂alkyl, C₂-C₁₂alkenyl, C₂-C₁₂alkynyl, C₃-C₈cycloalkyl or benzyl,reacting a compound of the formula (I) obtained, for example, inaccordance with process variant (k) with a compound of the formulaQ-C₁-C₁₂alkyl, Q-C₂-C₁₂alkenyl, Q-C₂-C₁₂alkynyl, Q-C₃-C₈cycloalkyl orQ-benzyl; in which Q is a leaving group; or

[0103] (m) for preparing a compound of the formula (I) in which R₅ is—C(═Y)—NH—R₈ and R₆ is hydrogen, and R₈ and Y are as defined above,reacting a compound of the above formula (Ia) with a compound of theformula (Y═)CNR₈; and, where appropriate

[0104] (n) reacting a resulting compound of the formula (I) in which qis 0 in analogy to process step (b) to give a compound in which q is 1.

[0105] The starting materials set out above and below of the formulae(III) to (XI) and (XIII) which [lacuna] for the preparation of thecompounds of the formula (I) are known or may be prepared byconventional methods. The compounds of the formulae (Ia), (II), (XII)and (XIV) are novel and are therefore likewise provided by theinvention. For the substituents of the compounds (Ia), (II), (XII) and(XIV), the same preferences apply as for the compounds of the formula(I).

[0106] The reactions described above and below are conducted in a mannerknown per se; for example in the absence or, where appropriate, in thepresence of a suitable solvent or diluent or a mixture thereof,operating where necessary with cooling, at room temperature or withheating, e.g. in a temperature range from about −80° C. to the boilingtemperature of the reaction mixture, preferably from about −20° C. toabout +150° C., and, where necessary, in a closed vessel, underpressure, in an inert gas atmosphere and/or under anhydrous conditions.Particularly advantageous reaction conditions may be inferred from theexamples.

[0107] Above and below, references to a leaving group or counterion areto be understood as meaning all eliminable groups which are commonlysuitable in chemical reactions, such as are known to the skilled worker;especially halogens such as fluorine, chlorine, bromine, iodine,—O—C(═O)—A, —O—P(═O)(W)₂, —O—Si(C₁-C₈alkyl)₃, —O—(C₁-C₈alkyl), —O-aryl,—O—S(═O)₂W, —S—P(═O)(W)₂, —S—P(═S)(W)₂, —S—S—(C₁-C₈alkyl), —S—S-aryl,—S—(C₁-C₈alkyl), —S-aryl, —S(═O)W, or —S(═O)₂W, in which W isunsubstituted or substituted C₁-C₈alkyl, C₂-C₈alkenyl, C₂-C₈alkynyl,unsubstituted or substituted aryl, unsubstituted or substituted benzyl,C₁-C₈alkoxy or di-(C₁-C₈alkyl)amine, in which the alkyl groups areindependent of one another; NO₃, NO₂, or sulfate, sulfite, phosphate,phosphite, carboxylate, imino ester, N₂ or carbamate; or, in the case ofcounterions, the anions of the said groups. A particularly preferredleaving group is chlorine or bromine, especially chlorine; or,respectively, chloride or bromide, especially chloride.

[0108] Examples of oxidizing agents used are inorganic peroxides, suchas sodium perborate, potassium permanganate or hydrogen peroxide; ororganic peracids, such as perbenzoic acid or peracetic acid, or mixturesof organic acids and hydrogen peroxide, such as acetic acid/hydrogenperoxide, for example.

[0109] The reaction of process (a) and (i) takes place preferably inalcohols, such as methanol or ethanol, for example, in a temperaturerange from 0° C. to +50° C., preferably at room temperature. A preferredreducing agent is sodium borohydride.

[0110] In process variants (b) and (n) it is preferred to use alcoholsas solvents, such as methanol or ethanol, for example. It is preferredto operate at from room temperature to 50° C.; suitable oxidizing agentsare those mentioned above, especially H₂O₂ or peracides, especiallyH₂O₂.

[0111] In the case of process variants (c) and (e) preference is givento using dialkyl ethers or tetrahydrofuran as solvents; the process isoperated in a temperature range from −70° C. to room temperature, andthe metallating agent used is magnesium or n-butyllithium.

[0112] In the case of process variant (d), inert solvents such asbenzene, toluene, xylenes, acetonitrile, propionitrile, ethyl acetate,propyl acetate, butyl acetate, acetone, diethyl ketone, methyl ethylketone, methyl isobutyl ketone, nitromethane or nitroethane, forexample, are used. The temperature range is situated from roomtemperature to the reflux of the corresponding solvent, the refluxtemperature being preferred.

[0113] In the case of process variant (f), the reducing agent used ispreferably triethylsilane in the presence of an acid, such astrifluoroacetic acid or trifluoromethanesulfonic acid, for example.

[0114] In the case of process variant (g), particularly suitablesolvents are dimethylformamide or tetrahydrofuran, preferablydimethylformamide; a preferred base is sodium hydride.

[0115] Process variant (j) is conducted preferably in an ether such astetrahydrofuran, for instance, and at room temperature.

[0116] In the case of process variants (k), (l) and (m), preferredsolvents used are apolar hydrocarbons, halogenated hydrocarbons such aschloroform or dichloromethane, for instance, or ethers such astetrahydrofuran or dioxane; and preferred bases used are tertiary aminessuch as triethylamine, for instance; or heterocyclic aromatics,preferably pyridine. Operation at room temperature is preferred.

[0117] Compounds of the formula (I) obtainable in accordance with theprocess or otherwise may be converted conventionally into othercompounds of the formula (I) by replacing one or more substituents ofthe starting compound of the formula (I) in conventional manner by oneor more other substituents in accordance with the invention.

[0118] Depending on the choice of particular suitable reactionconditions and starting materials, it is possible in one reaction stepto replace only one substituent by another substituent in accordancewith the invention, or in the same reaction step it is possible toreplace two or more substituents by other substituents in accordancewith the invention.

[0119] Salts of compound [sic] of the formula (I) may be preparedconventionally. For example, salts of compounds of the formula (I) withbases are obtained by treating the free compounds with an appropriatebase or an appropriate ion exchange reagent.

[0120] Salts of compounds of the formula (I) may be convertedconventionally into the free compounds of the formula (I) by means, forexample, of treatment with a suitable acid or a suitable ion exchangereagent.

[0121] Salts of compounds of the formula (I) may be transformedconventionally into other salts of a compound of the formula (I).

[0122] The compounds of the formula (I) in free form or in salt form maybe present in the form of one of the possible isomers or as a mixturethereof: for example, depending on the number, absolute and relativeconfiguration of asymmetric carbon atoms in the molecule and/or on theconfiguration of nonaromatic double bonds in the molecule, as pureisomers, such as enantiomers and/or diastereomers, or as isomermixtures, such as enantiomer mixtures, e.g. racemates, diastereomermixtures or racemate mixtures. The invention relates both to the pureisomers and to all possible isomer mixtures and should be understoodaccordingly in each case above and below, even if stereochemical detailsare not mentioned specifically in each case.

[0123] Diastereomer mixtures, racemate mixtures and mixtures ofdouble-bond isomers of compounds of the formula (I) in free form or insalt form, obtainable in accordance with the process—depending on thechoice of starting materials and procedures—or otherwise may be resolvedinto the pure diastereomers or racemates in a known way on the basis ofthe physicochemical differences of the constituents, for example byfractional crystallization, distillation and/or chromatography.

[0124] Enantiomer mixtures obtainable accordingly, such as racemates,may be separated into the optical isomers by known methods, for exampleby recrystallization from an optically active solvent, by chromatographyon chiral adsorbents, for example high-performance liquid chromatography(HPLC) on acetylcellulose, with the aid of suitable microorganisms, bycleavage with specific immobilized enzymes, via the formation ofinclusion compounds, for example using chiral crown ethers, in whichcase only one enantiomer is complexed, or by conversion intodiastereomeric salts and separation of the diastereomer mixture obtainedin this way, for example by fractional crystallization on the basis oftheir different solubilities into the diastereomers, from which thedesired enantiomer may be liberated by the action of appropriate agents.

[0125] Apart from by resolving corresponding isomer mixtures, purediastereomers and enantiomers, respectively, may also be obtained inaccordance with the invention by commonly known methods ofdiastereoselective or enantioselective synthesis, for example byperforming the process of the invention with starting materials ofappropriate stereochemistry.

[0126] The biologically more active isomer, for example enantiomer ordiastereomer, or isomer mixture, for example enantiomer mixture ordiastereomer mixture, is advantageously isolated and/or synthesized,where the individual components possess different biological activity.

[0127] The compounds of formula (I) in free form or in salt form mayalso be obtained in the form of their hydrates and/or may include othersolvents, examples being those used, where appropriate, for thecrystallization of compounds present in solid form.

[0128] The invention relates to all those embodiments of the processwhich start from a compound obtainable at any stage of the process as astarting product or intermediate and in which all or some of the absentsteps are carried out or a starting material is used in the form of aderivative and/or salt and/or its racemates and/or enantiomers or inparticular is formed under the reaction conditions.

[0129] In the process of the present invention, it is preferred to usethose starting materials and intermediates, in each case in free form orin salt form, which lead to the compound of the formula (I) described atthe outset as being particularly valuable, and, respectively, the saltsthereof.

[0130] The invention relates in particular to the preparation processdescribed in Example H1.

[0131] The compounds of the invention of the formula (I) arepreventively and/or curatively valuable active ingredients having a veryfavourable biocidal spectrum in the field of pest control, even at lowuse concentrations, while being favourably tolerated by homeotherms,fish and plants. The active ingredients of the invention are activeagainst all or individual development stages of normally sensitive, butalso resistant, animal pests, such as insects or representatives of theorder Acarina. The insecticidal or acaricidal action of the activeingredients of the invention may be manifested directly i.e. in thedeath of the pests, which occurs directly or only after a certain time,for example during ecdysis, or indirectly, for example in reducedoviposition and/or hatching rate, the good action corresponding to akill rate (mortality) of at least 50 to 60%.

[0132] Examples of the animal pests mentioned include those which areset out in the European Patent Application EP-A-736 252 page 5 line 55to page 6, line 55. The pests mentioned therein are thereforeincorporated by reference in the present invention's subject-matter. Theactive ingredients of the invention are especially suitable for thecontrol of Boophilus microplus, Nilaparvata lugens and Tetranychusurticae, preferably for the control of these pests in vegetable, fruitand rice cultures.

[0133] The active ingredients of the invention may be used in particularto control pests of the type mentioned which occur on plants, especiallyon useful plants and ornamentals, in agriculture, in horticulture and inforestry, or on parts of such plants, such as fruits, flowers, foliage,stems, tubers or roots, such control meaning containment or destruction,with the protection against these pests in some cases also extending toplant parts which are formed at a later point in time.

[0134] Particularly suitable target cultures include cereals, such aswheat, rye, barley, oats, rice, maize or sorghum; beet, such as sugarbeet or fooder beet; fruit, for example pome fruit, stone fruit and softfruit, such as apples, pears, plums, peaches, almonds, cherries orberries, for example strawberries, raspberries or blackberries; pulses,such as beans, lentils, peas or soya beans; oil crops, such as oil seedrape, mustard, poppies, olives, sunflowers, coconut, caster-oil plant,cacao or peanuts; cucurbits, such as squash, cucumbers or melons; fibrecrops, such as cotton, flax, hemp or jute; citrus fruits, such asoranges, lemons, grapefruit or tangerines; vegetables, such as spinach,lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes orcapsicum; Lauraceae, such as avocado, cinnamon or camphor; and alsotobacco, nuts, coffee, egg plants, sugar cane, tea, pepper, grapevines,hops, Musaceae, latex plants and ornamentals.

[0135] Further fields of use of the active ingredients of the inventionare in the protection of stored products and stores and of material andalso in the hygiene sector, in particular the protection of domesticanimals and livestock against pests of the type mentioned.

[0136] The invention therefore also relates to pesticide compositions(pesticides), such as—to be chosen in accordance with the intendedobjectives and prevailing circumstances—emulsifiable concentrates,suspension concentrates, directly sprayable or dilutable solutions,spreadable pastes, dilute emulsions, sprayable powders, soluble powders,dispersible powders, wettable powders, dusts, granules or encapsulationsin polymeric materials, which comprise at least one of the activeingredients of the invention.

[0137] In these compositions the active ingredient is used in straightform, a solid active ingredient for example in a specific particle size,or, preferably, together with at least one of the auxiliaries common inthe art of formulation, such as extenders, for example solvents or solidcarriers, or such as surface-active compounds (surfactants).

[0138] Examples of formulating auxiliaries used include solid carriers,solvents, stabilizers, slow release auxiliaries, colorants, and, whereappropriate, surface-active substances (surfactants). Suitable carriersand auxiliaries here include all of the substances commonly used inplant protection compositions, especially slug and snail controlcompositions (molluscicides). Suitable auxiliaries, such as solvents,solid carriers, surface-active compounds, nonionic surfactants, cationicsurfactants, anionic surfactants and further auxiliaries, in thecompositions used in accordance with the invention are for example thesame as those described in EP-A-736 252 they are incorporated byreference in the present invention's subject-matter.

[0139] The compositions generally include from 0.1 to 99%, in particularfrom 0.1 to 95%, of active ingredient and from 1 to 99.9%, in particularfrom 5 to 99.9%, of at least one solid or liquid auxiliary, it beingpossible in general for from 0 to 25%, in particular from 0.1 to 20%, ofthe compositions to comprise surfactants (% denotes in each case percentby weight). While concentrated compositions tend to be the preferredcommercial product, the end user generally uses dilute compositions withsubstantially lower active ingredient concentrations. Preferredcompositions are made up in particular as follows (%=percent by weight):Emulsifiable concentrates: Active ingredient: 1 to 95%, preferably 5 to20% Surfactant: 1 to 30%, preferably 10 to 20% Solvent: 5 to 98%,preferably 70 to 85% Dusts: Active ingredient: 0.1 to 10%, preferably0.1 to 1% Solid carrier: 99.9 to 90%, preferably 99.9 to 99% Suspensionconcentrates: Active ingredient: 5 to 75%, preferably 10 to 50% Water:94 to 24%, preferably 88 to 30% Surfactant: 1 to 40%, preferably 2 to30% Wettable powders: Active ingredient: 0.5 to 90%, preferably 1 to 80%Surfactant: 0.5 to 20%, preferably 1 to 15% Solid carrier: 5 to 99%,preferably 15 to 98% Granules: Active ingredient: 0.5 to 30%, preferably3 to 15% Solid carrier: 99.5 to 70%, preferably 97 to 85%

[0140] The action of the compositions of the invention may besubstantially broadened and adapted to prevailing circumstances throughthe addition of other active insecticidal ingredients. Suitable activeingredient additions include, for example, representatives from thefollowing classes of active ingredient: organophosphorus compounds,nitrophenols and derivatives, formamidines, acylureas, carbamates,pyrethroids, nitroenamines and derivatives, pyrroles, thioureas andderivatives, chlorinated hydrocarbons, and Bacillus thuringiensispreparations. The compositions of the invention may also comprisefurther solid or liquid auxiliaries, such as stabilizers, for exampleunepoxidized or epoxidized vegetable oils (e.g. epoxidized coconut oil,rapeseed oil or soya bean oil), defoamers, for example silicone oil,preservatives, viscosity regulators, binders and/or tackifiers, and alsofertilizers or other active ingredients for achieving specific effects,examples being acaricides, bactericides, fungicides, nematocides,molluscicides or selective herbicides.

[0141] The compositions of the invention are prepared in a known way, inthe absence of auxiliaries for example by grinding, sieving and/orcompressing a solid active ingredient or mixture of active ingredients,for example to a particular particle size, and in the presence of atleast one auxiliary for example by intimate mixing and/or grinding ofthe active ingredient or mixture of active ingredients with theauxiliary or auxiliaries. These processes for preparing the compositionsof the invention and the use of the compounds I to prepare thesecompositions are likewise provided by the invention.

[0142] The application techniques for the compositions, i.e. the methodsof controlling pests of the abovementioned type, such as spraying,fogging, dusting, brushing, dressing, scattering or pouring, which areto be chosen in accordance with the desired objectives and prevailingcircumstances, and the use of the compositions for controlling pests ofthe abovementioned type, are also provided by the invention. Typical useconcentrations are between 0.1 and 1000 ppm, preferably between 0.1 and500 ppm, of active ingredient. The application rates per hectare aregenerally from 1 to 2000 g of active ingredient per hectare, inparticular from 10 to 1000 g/ha, preferably from 20 to 600 g/ha.

[0143] A preferred application technique in the field of crop protectionis that of application to the foliage of the plants (foliarapplication), the frequency and rate of application being guided by theintensity of infestation of the pest in question. However, the activeingredient may also pass into the plants through the root system(systemic action), by the locus of the plants being drenched with aliquid composition or the active ingredient in solid form beingincorporated into the locus of the plants, for example into the soil, inthe form for example of granules (soil application). In the case ofpaddy rice cultures, such granules may be added to the flooded paddyfield.

[0144] The compositions of the invention are also suitable forprotecting plant propagation material, including genetically modifiedpropagation material, for example seed, such as fruits, tubers orkernels, or plant cuttings, against animal pests. The propagationmaterial may be treated with the composition prior to planting; seed,for example, may be dressed before sowing. The active ingredients of theinvention may also be applied to seed kernels (coating) by eitherdrenching the kernels in a liquid composition or coating them with asolid composition. The composition may also be applied to the site ofapplication when the propagation material is being applied, for exampleto the seed furrow at the time of sowing. These treatment methods forplant propagation material, and the plant propagation material thustreated, are further provided by the invention.

[0145] The examples which follow serve to illustrate the invention. Theydo not restrict the invention. Temperatures are stated in degreesCelsius, proportions of solvents in volume fractions.

PREPARATION EXAMPLES EXAMPLE H1 Preparation of the Compound of theFormula

[0146]

[0147] H1a) Preparation of the Compound of the Formula

[0148] A solution of 100 g of 4-bromobenzotrifluoride in 600 ml oftetrahydrofuran is admixed dropwise at −60° C. with 278 ml ofn-butyllithium (1.6 molar n-hexane solution) and the reactiontemperature is allowed to rise to −40° C. Then at −65° C. 20.2 ml ofethyl isonicotinate are added dropwise over the course of one hourfollowed by stirring for a further hour at 0° C. The reaction mixture isthen hydrolysed with 300 ml of acetic acid (10%), the water phase isseparated off and the organic phase is washed with sodium chloridesolution, dried over sodium sulfate and concentrated under reducedpressure. The residue is filtered over silica gel (eluent: tert-butylmethyl ether/hexane=3:1). This gives the compound (A) having a meltingpoint of 160-163° C.

[0149] H1b) Preparation of the Compound of the Formula

[0150] 15.9 g of the compound (A) and 7.2 g of 4-nitrobenzyl chlorideare stirred in 200 ml of nitromethane at 110° C. for 48 hours. Thereaction mixture is then concentrated under reduced pressure and theresidue is crystallized from dichloromethane/tert-butyl methylether:beige crystals. This gives the compound (B) having a melting point of202-204° C.

[0151] H1c): Preparation of the Compound of the Formula

[0152] 19.1 g of the compound (B) in 400 ml of methanol are admixed inportions with 1.91 g of sodium borohydride and the mixture is stirredfor 1 hour. Following the addition of 5 ml of acetone, the reactionmixture is concentrated under reduced pressure, the residue is stirredwith tert-butyl methyl ether/water and the water phase is separated off.The organic phase is washed with sodium chloride, dried (sodium sulfate)and concentrated under reduced pressure. The residue is filtered oversilica gel (tert-butyl methyl ether/hexane=1.1): This gives the compound(C) as a resin.

[0153] H1d) Preparation of the Compound of the Formula

[0154] A solution of 15 g of compound (C) in 150 ml of tetrahydrofuranis stirred in the presence of 7.5 g of Raney nickel in a hydrogenatmosphere for 18 hours at room temperature under atmospheric pressure.The catalyst is filtered off and the solvent is distilled off underreduced pressure at a maximum bath temperature of 40° C. This gives thecompound (D) as a foam.

[0155] H1e) Preparation of the Title Compound

[0156] 2.03 g of the compound (D) in 50 ml of dichloromethane areadmixed with 0.48 ml of pyridine and 0.47 ml of propargyl chloroformateand the mixture is stirred for 2 hours. The reaction mixture is thenstirred with 50 ml of dichloromethane and 50 ml of water, the waterphase is separated off and the organic phase is dried over sodiumsulfate and concentrated under reduced pressure. The residue ischromatographed on silica gel using dichloromethane/methanol=19:1. Thisgives the title compound as a foam. (Compound 1.1)

EXAMPLE H2 Preparation of the Compound of the Formula

[0157]

[0158] 1.41 g of the compound prepared in Example H1) in 40 ml ofmethanol are stirred at 50° C. together with 7.4 ml of 30% hydrogenperoxide solution for 24 hours. Ethyl acetate is added to the reactionmixture, which is washed with water and sodium chloride solution, dried(sodium sulfate) and concentrated under reduced pressure. The product isrecrystallized from dichloromethane/tert-butyl methyl ether. This givesthe title compound with a melting point of 142-145° C. (decomposition).(Compound 1.2)

EXAMPLE H3 Preparation of the Compound of the Formula

[0159]

[0160] 2.03 g of the compound (D) in 50 ml of dichloromethane areadmixed with 0.1 ml of triethylamine and 0.43 ml of isopropyl isocyanateand the mixture is stirred for 72 hours. The reaction mixture isconcentrated under reduced pressure and the residue is chromatographedon silica gel using dichloromethane/methanol=19:1. This gives the titlecompound as a foam (Compound 1.11).

EXAMPLE H4 Preparation of the Compound of the Formula

[0161]

[0162] 1 g of the compound prepared according to Example H3) in 30 ml ofmethanol is stirred at 50° C. together with 5.2 ml of 30% hydrogenperoxide solution for 24 hours. Ethyl acetate is added to the reactionmixture, which is washed with water and sodium chloride solution, dried(sodium sulfate) and concentrated under reduced pressure. Fromdichloromethane/hexane the title compound is thus obtained, with amelting point of 172-174° C. (decomposition, Compound 1.12).

EXAMPLE H5 Preparation of the Compound of the Formula

[0163]

[0164] A mixture of 2.03 g of compound (D), 2.81 ml of triethylamine,1.12 g of 4-fluorophenylboric acid and 1.09 g of copper(II) acetate in50 ml of dichloromethane is stirred at room temperature for 96 hours.The reaction mixture is subsequently filtered and concentrated underreduced pressure and the residue is chromatographed on silica gel usingethyl acetate/hexane=3:2. This gives the title compound as a foam(Compound 1.33).

EXAMPLE H6

[0165] In a manner analogous to that described above, the furthercompounds of the following tables may also be prepared. In the tables,Smpt. denotes the melting point in ° C., Me denotes methyl, Et ethyl,i-Prop. isopropyl, i-But. iso-butyl and c-Prop. cyclopropyl. TABLE 1Compounds of the formula

Ex. No. R₄ R₅ Q Melting point 1.1 H —COOCH₂—C≡CH 0 Foam 1.2 H—COOCH₂—C≡CH 1 142-145° C. (decomp.) 1.3 H COSEthyl 0 Foam 1.4 HCOSEthyl 1 1.5 H CONHMethyl 0 1.6 H CONHMethyl 1 1.7 H CONHEthyl 0 1.8 HCONHEthyl 1 1.9 H CONH-n-Propyl 0 1.10 H CONH-n-Propyl 1 1.11 HCONH-i-Propyl 0 Foam 1.12 H CONH-i-Propyl 1 172-174° C. (decomp.) 1.13 HCSNH-Methyl 0 1.14 H CSNH-Methyl 1 1.15 H CSNH-Ethyl 0 1.16 H CSNH-Ethyl1 1.17 H CO-Methyl 0 1.18 H CO-Methyl 1 1.19 H CO-Ethyl 0 Foam 1.20 HCO-Ethyl 1 190-193° C. 1.21 H CO—CH₂Cl 0 1.22 H CO—CH₂—OCH₃ 0 1.23 HCO—CH₂—OCH₃ 1 1.24 H CO—CH₂—SCH₃ 0 1.25 H CO—CH₂—SCH₃ 1 1.26 H SO₂CH₃ 01.27 H SO₂CH₃ 1 1.28 H SO₂Ethyl 0 1.29 H SO₂Ethyl 1 1.30 H SO₂CF₃ 0 1.31H SO₂CF₃ 1 1.32 H Phenyl 0 1.33 H 4-F-Phenyl 0 Foam 1.34 H 3-CF₃-Phenyl0 1.35 H 4-CF₃-Phenyl 0 1.36 H 4-OCF₃-Phenyl 0 1.37 H 4-Cl-Phenyl 0 1.38CH₃ —COOCH₂—C≡CH 0 227-230° C. 1.39 CH₃ —COOCH₂—C≡CH 1 1.40 CH₃CONH-i-Propyl 0′ 1.41 CH₃ CONH-i-Propyl 1 1.42 OCH₃ —COOCH₂—C≡CH 0156-166° C. 1.43 OCH₃ —COOCH₂—C≡CH 1 1.44 OCH₃ CONH-i-Propyl 0 1.45 OCH₃CONH-i-Propyl 1 1.46 H CSNH-i-Propyl 0 1.47 H CSNH-i-Propyl 1

[0166] TABLE 2 Compounds of the formula

Ex. No. R₄ R₅ Q Melting point 2.1 H —COOCH₂—C≡CH 0 2.2 H —COOCH₂—C≡CH 12.3 H COSEthyl 0 2.4 H COSEthyl 1 2.5 H CONHMethyl 0 2.6 H CONHMethyl 12.7 H CONHEthyl 0 2.8 H CONHEthyl 1 2.9 H CONH-n-Propyl 0 2.10 HCONH-n-Propyl 1 2.11 H CONH-i-Propyl 0 2.12 H CONH-i-Propyl 1 2.13 HCSNH-Methyl 0 2.14 H CSNH-Methyl 1 2.15 H CSNH-Ethyl 0 2.16 H CSNH-Ethyl1 2.17 H CO-Methyl 0 2.18 H CO-Methyl 1 2.19 H CO-Ethyl 0 2.20 HCO-Ethyl 1 2.21 H CO—CH₂Cl 0 2.22 H CO—CH₂—OCH₃ 0 2.23 H CO—CH₂—OCH₃ 12.24 H CO—CH₂—SCH₃ 0 2.25 H CO—CH₂—SCH₃ 1 2.26 H SO₂CH₃ 0 2.27 H SO₂CH₃1 2.28 H SO₂Ethyl 0 2.29 H SO₂Ethyl 1 2.30 H SO₂CF₃ 0 2.31 H SO₂CF₃ 12.32 H Phenyl 0 2.33 H 4-F-Phenyl 0 2.34 H 3-CF₃-Phenyl 0 2.35 H4-CF₃-Phenyl 0 2.36 H 4-OCF₃-Phenyl 0 2.37 H 4-Cl-Phenyl 0 2.38 OH3—COOCH₂—C≡CH 0 2.39 CH3 —COOCH₂—C≡CH 1 2.40 OH3 CONH-i-Propyl 0′ 2.41OH3 CONH-i-Propyl 1 2.42 00H3 —COOCH₂—C≡CH 0 2.43 OCH3 —COOCH₂—C≡CH 12.44 00H3 CONH-i-Propyl 0 2.45 OCH3 CONH-i-Propyl 1 2.46 H CSNH-i-Propyl0 2.47 H CSNH-i-Propyl 1

[0167] TABLE A Compounds of the formula

(Ib), and of the formula

(Ic) No. R₄ R₅ R₆ A.1 H —COOCH₂—C≡CH H A.2 H —COOCH₂—C≡CH CH₃ A.3 HCOSEthyl H A.4 H COSEthyl CH₃ A.5 H CONHMethyl H A.6 H CONHMethyl CH₃A.7 H CONHEthyl H A.8 H CONHEthyl CH₃ A.9 H CONH-n-Propyl H A.10 HCONH-n-Propyl CH₃ A.11 H CONH-i-Propyl H A.12 H CONH-i-Propyl CH₃ A.13 HCSNH-Methyl H A.14 H CSNH-Methyl CH₃ A.15 H CSNH-Ethyl H A.16 HCSNH-Ethyl CH₃ A.17 H CO-Methyl H A.18 H CO-Methyl CH₃ A.19 H CO-Ethyl HA.20 H CO-Ethyl CH₃ A.21 H CO—CH₂Cl H A.22 H CO—CH₂Cl CH₃ A.23 HCO—CH₂—OCH₃ H A.24 H CO—CH₂—OCH₃ CH₃ A.25 H CO—CH₂—SCH₃ H A.26 HCO—CH₂—SCH₃ CH₃ A.27 H SO₂CH₃ H A.28 H SO₂CH₃ CH₃ A.29 H SO₂Ethyl H A.30H SO₂Ethyl CH₃ A.31 H SO₂CF₃ H A.32 H SO₂CF₃ CH₃ A.33 H Phenyl H A.34 HPhenyl CH₃ A.35 H 4-F-Phenyl H A.36 H 4-F-Phenyl CH₃ A.37 H 3-CF₃-PhenylH A.38 H 3-CF₃-Phenyl CH₃ A.39 H 4-CF₃-Phenyl H A.40 H 4-CF₃-Phenyl CH₃A.41 H 4-OCF₃-Phenyl H A.42 H 4-OCF₃-Phenyl CH₃ A.43 H 4-Cl-Phenyl HA.44 H 4-Cl-Phenyl CH₃ A.45 CH3 —COOCH₂—C≡CH H A.46 CH3 —COOCH₂—C≡CH CH₃A.47 CH3 CONH-i-Propyl H A.48 CH3 CONH-i-Propyl CH₃ A.49 OCH3—COOCH₂—C≡CH H A.50 OCH3 —COOCH₂—C≡CH CH₃ A.51 OCH3 CONH-i-Propyl H A.52OCH3 CONH-i-Propyl CH₃ A.53 H CSNH-i-Propyl H A.54 H CSNH-i-Propyl CH₃

[0168] Table 3:

[0169] Compounds of the general formula (Ib) in which R₁ and R₂ are CF₃and R₃ is H and the combination of the substituents R₄, R₅ and R₆ forone compound corresponds in each case to a line A.1 to A.54 in Table A.

[0170] Table 4:

[0171] Compounds of the general formula (Ib) in which R₁ and R₂ are CF₃and R₃ is OH and the combination of the substituents R₄, R₅ and R₆ forone compound corresponds in each case to a line A.1 to A.54 in Table A.

[0172] Table 5:

[0173] Compounds of the general formula (Ib) in which R₁ and R₂ are CF₃and R₃ is F and the combination of the substituents R₄, R₅ and R₆ forone compound corresponds in each case to a line A.1 to A.54 in Table A.

[0174] Table 6:

[0175] Compounds of the general formula (Ib) in which R₁ and R₂ are CF₃and R₃ is OCH₃ and the combination of the substituents R₄, R₅ and R₆ forone compound corresponds in each case to a line A.1 to A.54 in Table A.

[0176] Table 7:

[0177] Compounds of the general formula (Ic) in which R₁ and R₂ are CF₃and R₃ is H and the combination of the substituents R₄, R₅ and R₆ forone compound corresponds in each case to a line A.1 to A.54 in Table A.

[0178] Table 8:

[0179] Compounds of the general formula (Ic) in which R₁ and R₂ are CF₃and R₃ is OH and the combination of the substituents R₄, R₅ and R₆ forone compound corresponds in each case to a line A.1 to A.54 in Table A.

[0180] Table 9:

[0181] Compounds of the general formula (Ic) in which R₁ and R₂ are CF₃and R₃ is F and the combination of the substituents R₄, R₅ and R₆ forone compound corresponds in each case to a line A.1 to A.54 in Table A.

[0182] Table 10:

[0183] Compounds of the general formula (Ic) in which R₁ and R₂ are CF₃and R₃ is OCH₃ and the combination of the substituents R₄, R₅ and R₆ forone compound corresponds in each case to a line A.1 to A.54 in Table A.

[0184] Table 11:

[0185] Compounds of the general formula (Ib) in which R₁ is CF₃, R₂ isOCF₃ and R₃ is H and the combination of the substituents R₄, R₅ and R₆for one compound corresponds in each case to a line A.1 to A.54 in TableA.

[0186] Table 12:

[0187] Compounds of the general formula (Ib) in which R₁ is CF₃, R₂ isOCF₃ and R₃ is OH and the combination of the substituents R₄, R₅ and R₆for one compound corresponds in each case to a line A.1 to A.54 in TableA.

[0188] Table 13:

[0189] Compounds of the general formula (Ib) in which R₁ is CF₃, R₂ isOCF₃ and R₃ is F and the combination of the substituents R₄, R₅ and R₆for one compound corresponds in each case to a line A.1 to A.54 in TableA.

[0190] Table 14:

[0191] Compounds of the general formula (Ib) in which R₁ is CF₃, R₂ isOCF₃ and R₃ is OCH₃ and the combination of the substituents R₄, R₅ andR₆ for one compound corresponds in each case to a line A.1 to A.54 inTable A.

[0192] Table 15:

[0193] Compounds of the general formula (Ic) in which R₁ is CF₃, R₂ isOCF₃ and R₃ is H and the combination of the substituents R₄, R₅ and R₆for one compound corresponds in each case to a line A.1 to A.54 in TableA.

[0194] Table 16:

[0195] Compounds of the general formula (Ic) in which R₁ is CF₃, R₂ isOCF₃ and R₃ is OH and the combination of the substituents R₄, R₅ and R₆for one compound corresponds in each case to a line A.1 to A.54 in TableA.

[0196] Table 17:

[0197] Compounds of the general formula (Ic) in which R₁ is CF₃, R₂ isOCF₃ and R₃ is F and the combination of the substituents R₄, R₅ and R₆for one compound corresponds in each case to a line A.1 to A.54 in TableA.

[0198] Table 18:

[0199] Compounds of the general formula (Ic) in which R₁ is CF₃, R₂ isOCF₃ and R₃ is OCH₃ and the combination of the substituents R₄, R₅ andR₆ for one compound corresponds in each case to a line A.1 to A.54 inTable A.

[0200] Table 19:

[0201] Compounds of the general formula (Ib) in which R₁ and R₂ are OCF₃and R₃ is H and the combination of the substituents R₄, R₅ and R₆ forone compound corresponds in each case to a line A.1 to A.54 in Table A.

[0202] Table 20:

[0203] Compounds of the general formula (Ib) in which R₁ and R₂ are OCF₃and R₃ is OH and the combination of the substituents R₄, R₅ and R₆ forone compound corresponds in each case to a line A.1 to A.54 in Table A.

[0204] Table 21:

[0205] Compounds of the general formula (Ib) in which R₁ and R₂ are OCF₃and R₃ is F and the combination of the substituents R₄, R₅ and R₆ forone compound corresponds in each case to a line A.1 to A.54 in Table A.

[0206] Table 22:

[0207] Compounds of the general formula (Ib) in which R₁ and R₂ are OCF₃and R₃ is OCH₃ and the combination of the substituents R₄, R₅ and R₆ forone compound corresponds in each case to a line A.1 to A.54 in Table A.

[0208] Table 23:

[0209] Compounds of the general formula (Ic) in which R₁ and R₂ are OCF₃and R₃ is H and the combination of the substituents R₄, R₅ and R₆ forone compound corresponds in each case to a line A.1 to A.54 in Table A.

[0210] Table 24:

[0211] Compounds of the general formula (Ic) in which R₁ and R₂ are OCF₃and R₃ is OH and the combination of the substituents R₄, R₅ and R₆ forone compound corresponds in each case to a line A.1 to A.54 in Table A.

[0212] Table 25:

[0213] Compounds of the general formula (Ic) in which R₁ and R₂ are OCF₃and R₃ is F and the combination of the substituents R₄, R₅ and R₆ forone compound corresponds in each case to a line A.1 to A.54 in Table A.

[0214] Table 26:

[0215] Compounds of the general formula (Ic) in which R₁ and R₂ are OCF₃and R₃ is OCH₃ and the combination of the substituents R₄, R₅ and R₆ forone compound corresponds in each case to a line A.1 to A.54 in Table A.

[0216] Table 27:

[0217] Compounds of the general formula (Ib) in which R₁ is CF₃, R₂ is Fand R₃ is H and the combination of the substituents R₄, R₅ and R₆ forone compound corresponds in each case to a line A.1 to A.54 in Table A.

[0218] Table 28:

[0219] Compounds of the general formula (Ib) in which R₁ is CF₃, R₂ is Fand R₃ is OH and the combination of the substituents R₄, R₅ and R₆ forone compound corresponds in each case to a line A.1 to A.54 in Table A.

[0220] Table 29:

[0221] Compounds of the general formula (Ib) in which R₁ is CF₃, R₂ is Fand R₃ is F and the combination of the substituents R₄, R₅ and R₆ forone compound corresponds in each case to a line A.1 to A.54 in Table A.

[0222] Table 30:

[0223] Compounds of the general formula (Ib) in which R₁ is CF₃, R₂ is Fand R₃ is OCH₃ and the combination of the substituents R₄, R₅ and R₆ forone compound corresponds in each case to a line A.1 to A.54 in Table A.

[0224] Table 31:

[0225] Compounds of the general formula (Ic) in which R₁ is CF₃, R₂ is Fand R₃ is H and the combination of the substituents R₄, R₅ and R₆ forone compound corresponds in each case to a line A.1 to A.54 in Table A.

[0226] Table 32:

[0227] Compounds of the general formula (Ic) in which R₁ is CF₃, R₂ is Fand R₃ is OH and the combination of the substituents R₄, R₅ and R₆ forone compound corresponds in each case to a line A.1 to A.54 in Table A.

[0228] Table 33:

[0229] Compounds of the general formula (Ic) in which R₁ is CF₃, R₂ is Fand R₃ is F and the combination of the substituents R₄, R₅ and R₆ forone compound corresponds in each case to a line A.1 to A.54 in Table A.

[0230] Table 34:

[0231] Compounds of the general formula (Ic) in which R₁ is CF₃, R₂ is Fand R₃ is OCH₃ and the combination of the substituents R₄, R₅ and R₆ forone compound corresponds in each case to a line A.1 to A.54 in Table A.

[0232] Table 35:

[0233] Compounds of the general formula (Ib) in which R₁ and R₂ are SCF₃and R₃ is H and the combination of the substituents R₄, R₅ and R₆ forone compound corresponds in each case to a line A.1 to A.54 in Table A.

[0234] Table 36:

[0235] Compounds of the general formula (Ib) in which R₁ and R₂ are SCF₃and R₃ is OH and the combination of the substituents R₄, R₅ and R₆ forone compound corresponds in each case to a line A.1 to A.54 in Table A.

[0236] Table 37:

[0237] Compounds of the general formula (Ib) in which R₁ and R₂ are SCF₃and R₃ is F and the combination of the substituents R₄, R₅ and R₆ forone compound corresponds in each case to a line A.1 to A.54 in Table A.

[0238] Table 38:

[0239] Compounds of the general formula (Ib) in which R₁ and R₂ are SCF₃and R₃ is OCH₃ and the combination of the substituents R₄, R₅ and R₆ forone compound corresponds in each case to a line A.1 to A.54 in Table A.

[0240] Table 39:

[0241] Compounds of the general formula (Ic) in which R₁ and R₂ are SCF₃and R₃ is H and the combination of the substituents R₄, R₅ and R₆ forone compound corresponds in each case to a line A.1 to A.54 in Table A.

[0242] Table 40:

[0243] Compounds of the general formula (Ic) in which R₁ and R₂ are SCF₃and R₃ is OH and the combination of the substituents R₄, R₅ and R₆ forone compound corresponds in each case to a line A.1 to A.54 in Table A.

[0244] Table 41:

[0245] Compounds of the general formula (Ic) in which R₁ and R₂ are SCF₃and R₃ is F and the combination of the substituents R₄, R₅ and R₆ forone compound corresponds in each case to a line A.1 to A.54 in Table A.

[0246] Table 42:

[0247] Compounds of the general formula (Ic) in which R₁ and R₂ are SCF₃and R₃ is OCH₃ and the combination of the substituents R₄, R₅ and R₆ forone compound corresponds in each case to a line A.1 to A.54 in Table A.

[0248] Formulation Examples (%=Percent by Weight) Example F1: Emulsionconcentrates a) b) c) Active ingredient 25% 40% 50% Calciumdodecylbenzenesulfonate  5%  8%  6% Castor oil polyethylene glycol ether(36 mol EO)  5% — — Tributylphenol polyethylene glycol ether — 12%  4%(30 mol EO) Cyclohexanone — 15% 20% Xylene mixture 65% 25% 20%

[0249] Mixing of finely ground active ingredient and additives gives anemulsion concentrate which provides emulsions of desired concentrationby dilution with water. Example F2: Solutions a) b) c) d) Activeingredient 80% 10%  5% 95% Ethylene glycol monomethyl ether 20% — — —Polyethylene glycol (MW 400) — 70% — — N-Methylpyrrolid-2-one — 20% — —Epoxidized coconut oil — —  1%  5% Petroleum spirit (boiling range:160-190°) — — 94% —

[0250] Mixing of finely ground active ingredient and additives gives asolution suitable for application in the form of very small droplets.Example F3: Granules a) b) c) d) Active ingredient  5% 10%  8% 21%Kaolin 94% — 79% 54% Highly disperse silica  1% — 13%  7% Attapulgite —90% — 18%

[0251] The active ingredient is dissolved in dichloromethane, thesolution is sprayed onto the carrier material mixture and the solvent isevaporated under reduced pressure.

Biological Examples EXAMPLE B1 Action Against Heliothis virescensCaterpillars

[0252] Young soya bean plants are sprayed with an aqueous emulsion sprayliquor containing 400 ppm of the active ingredient. After the spraycoating has dried on, the soya bean plants are populated with 10first-stage caterpillars of Heliothis virescens and placed in a plasticcontainer. Evaluation takes place 6 days later. The percentage reductionin population, or the percentage reduction in feeding damage (% action),is determined by comparing the number of dead caterpillars and thefeeding damage on the treated plants with those on the untreated plants.The compounds of the tables exhibit a good action against Heliothisvirescen s in this test. In particular, compounds 1.1, 1.2, 1.38 and1.42 display an action of more than 80%.

EXAMPLE B2 Action Against Plutella xvlostella Caterpillars

[0253] Young cabbage plants are sprayed with an aqueous emulsion sprayliquor containing 400 ppm of the active ingredient. After the spraycoating has dried on, the cabbage plants are populated with 10third-stage caterpillars of Plutella xylostella and placed in a plasticcontainer. Evaluation takes place 3 days later. The percentage reductionin population, or the percentage reduction in feeding damage (% action),is determined by comparing the number of dead caterpillars and thefeeding damage on the treated plants with those on the untreated plants.The compounds of the tables exhibit a good action against Plutellaxylostella in this test. In particular, compounds 1.1, 1.2, 1.38 and1.42 display an action of more than 80%.

EXAMPLE B3 Action Against Diabrotica balteata Larvae

[0254] Maize seedlings are sprayed with an aqueous emulsion spray liquorcontaining 400 ppm of the active ingredient. After the spray coating hasdried on, the maize seedlings are populated with 10 second-stage larvaeof Diabrotica balteata and placed in a plastic container. Evaluationtakes place 6 days later. The percentage reduction in population (%action) is determined by comparing the number of dead larvae on thetreated plants with those on the untreated plants. The compounds of thetables exhibit a good action against Diabrotica balteatain this test. Inparticular, compounds 1.1, 1.2, 1.38 and 1.42 display an action of morethan 80%.

1. A compound of the formula

in which R₁ and R₂ independently of one another are halogen, C₁-C₆alkyl,halo-C₁-C₆alkyl, C₁-C₆alkoxy, halo-C₁-C₆alkoxy, —S(═O)_(p)-R₉ or SF₅, R₃is hydrogen, OH, halogen, C₁-C₆alkoxy or —O—C(═O)—C₁-C₆alkyl, R₄ ishydrogen, halogen, C₁-C₆alkyl, halo-C₁-C₆alkyl, C₁-C₆alkoxy,halo-C₁-C₆alkoxy, —S(═O)_(p)-R₉ or SCN; R₅ and R₆ independently of oneanother are hydrogen, C₁-C₁₂alkyl, halo-C₁-C₁₂alkyl, C₂-C₁₂alkenyl,halo-C₂-C₁₂alkenyl, C₂-C₁₂alkynyl, halo-C₂-C₁₂alkynyl, C₃-C₈cycloalkyl,—C(═O)—O—R₇, —C(═S)—O—R₈, —C(═Y)—Z—R₈, —S(═O)_(p)-R₉, aryl,aryl-C₁-C₆alkyl, heterocyclyl or heterocyclyl-C₁-C₆alkyl; or, dependingon substitution possibilities on the ring are C₃-C₈cycloalkyl, aryl,aryl-C₁-C₆alkyl, heterocyclyl or heterocyclyl-C₁-C₆alkyl, substitutedfrom one to five times independently of one another by halogen,hydroxyl, cyano, nitro, C₁-C₆alkyl, halo-C₁-C₆alkyl, C₁-C₆alkoxy orhalo-C₁-C₆alkoxy; or in common, together with the nitrogen atom to whichthey are attached, form a heterocyclic ring which is unsubstituted orsubstituted; Y is oxygen or sulfur; Z is a bond, —NR₁₀— or sulfur; R₇ isC₁-C₆alkoxy-C₁-C₆alkyl, C₁-C₆alkylthio-C₁-C₆alkyl,C₁-C₆alkylamino-C₁-C₆alkyl, C₃-C₆alkynyl,C₁-C₆alkyl-S(═O)_(p)-C₁-C₆alkyl, C₃-C₈cycloalkyl, aryl, aryl-C₁-C₆alkyl,heterocyclyl or heterocyclyl-C₁-C₆alkyl; or, depending on substitutionpossibilities on the ring is C₃-C₈cycloalkyl, aryl, aryl-C₁-C₆alkyl,heterocyclyl or heterocyclyl-C₁-C₆alkyl, substituted from one to fivetimes independently of one another by halogen, cyano, nitro, C₁-C₆alkyl,halo-C₁-C₆alkyl, C₁-C₆alkoxy or halo-C₁-C₆alkoxy; R₈ is C₁-C₆alkyl,halo-C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkyl, C₁-C₆alkylthio-C₁-C₆alkyl,C₂-C₆alkenyl, C₃-C₆alkynyl, C₁-C₆alkyl-S(═O)_(p)-C₁-C₆alkyl,C₃-C₈cycloalkyl, aryl, aryl-C₁-C₆alkyl, heterocyclyl orheterocyclyl-C₁-C₆alkyl; or, depending on substitution possibilities onthe ring is C₃-C₈cycloalkyl, aryl, aryl-C₁-C₆alkyl, heterocyclyl orheterocyclyl-C₁-C₆alkyl, substituted from one to five timesindependently of one another by halogen, cyano, nitro, C₁-C₆alkyl,halo-C₁-C₆alkyl, C₁-C₆alkoxy or halo-C₁-C₆alkoxy; R₉ is C₁-C₆alkyl,C₃-C₈cycloalkyl, halo-C₁-C₆alkyl or benzyl; R₁₀ is hydrogen, C₁-C₆alkyl,C₃-C₈cycloalkyl, halo-C₁-C₆alkyl or benzyl; p is 0, 1 or 2; and q is 0or 1; and, where appropriate, E/Z isomers, E/Z isomer mixtures and/ortautomers, each in free form or in salt form.
 2. A compound according toclaim 1 of the formula (I) in free form.
 3. A compound according toeither of claims 1 or 2 of the formula (I) in which R₁ and R₂independently of one another are halogen, C₁-C₂alkyl, halo-C₁-C₂alkyl,C₁-C₂alkoxy or halo-C₁-C₂alkoxy.
 4. A pesticide composition whichcomprises at least one compound according to claim 1 of the formula (I),in free form or in agrochemically useable salt form, as activeingredient and at least one auxiliary.
 5. A process for preparing acomposition as described in claim 4, which comprises intimately mixingthe active substance with the auxiliary or auxiliaries.
 6. A method ofcontrolling pests, which comprises applying a pesticidal composition asdescribed in claim 4 to the pests or their habitat.
 7. The use of thecompound according to any one of claims 1 to 3 of the formula (I), infree form or, where appropriate, in agrochemically useable salt form,for preparing a composition as described in claim 4.